The present invention relates to 2,2,6-trimethyl-1-cyclohexen-1-ylacetaldehyde enol esters (or beta-cyclohomocitral enol esters) produced by the novel processes of our inventions, and novel compositions using one or more of such beta-cyclohomocitral enol esters to alter, modify or enhance the flavor and/or armoa of consumable materials or impart flavor and/or armoa to consumable materials.
There has been considerable work performed relating to substances which can be used to impart (modify, augment or enhance) flavors and fragrances to (or in) various consumable materials. These substances are used to diminish the use of natural materials, some of which may be in short supply and to provide more uniform properties in the finished product. Sweet, sweet vegetable, fruity, raspberry, ionone-like, rosey and raspberry seed aromas as well as sweet, sweet vegetable, sweet carrot juice, fruity, raspberry, ionone-like, woody, and raspberry kernel tastes with sweet aftertastes are particularly desirable for many uses in foodstuff flavors, chewing gum flavors, toothpaste flavors and medicinal product flavors. Sweet, floral and fruity notes are desirable in several types of perfume compositions. Sweet, floral and fruity notes are desirable in tobacco flavoring compositions.
Arctander, "Perfume and Flavor Chemicals", 1969 discloses the use in perfume compositions and flavors of "cyclocitral", "dehydro-beta-cyclocitral", "isocyclocitral", "alpha-cyclocitrylidene acetaldehyde" and "beta-cyclocitrylidene acetaldehyde", thus:
i. "760 CYCLOCITRAL
Alpha-cyclocitral = (2,2,6-trimethyl-5-cyclohexen-1-carboxaldehyde).
beta-cyclocitral = (2,2,6-trimethyl-6-cyclohexen-1-carboxaldehyde). Both isomers are known and have been produced separately. ##STR2##
Very rarely offered commercially. These particular cyclocitrals have little or no interest to the creative perfumer, but they have served as part of many pieces of proof that isomers (alpha-beta) do often have different odors."
ii. "761: iso-CYCLOCITRAL
A mixture of two chemicals: 3,5,6-trimethyl-3-cyclohexen-1-carboxaldehyde (meta-cyclocitral). ##STR3##
2,4,6-trimethyl-4-cyclohexen-1-carboxaldehyde (symmetric-iso-cyclocitral). ##STR4##
Powerful, and diffusive, foliage-green, "dark" weedy and dry odor, sometimes described as "Flower-shop odor". The earthy and wet green notes are quite natural in high dilution and resemble the odor of stems from plants and flowers fresh from the soil.
Finds use in perfume compositions where it blends excellently with Oakmoss products (compensates for sweetness and lifts the topnote), with Ionones (freshness), Geranium and Galbanum (enhances the green and "vegetable" notes ), etc. . . . "
iii. "762: alpha CYCLOCITRYLIDENE ACETALDEHYDE ##STR5##
Mild, floral-woody, somewhat oily-herbaceous odor, remotely reminiscent of Rose with similarity to the odor of hydrogenated Ionones.
Suggested for use in perfume compositions. It brings a certain amount of floral lift to Rose compositions, and performs fairly well even in soap. However, the cost of the rarely offered and never readily available lots are rather discouraging to the perfumer, and it is most conceivable that this material can be left out of the perfumer's library without any great loss. . . . "
iv. "763: beta-CYCLOCITRYLIDENE ACETALDEHYDE
2,6,6-trimethyl-l-cyclohexenyl-beta-acrolein. ##STR6##
Sweet-woody, rather heavy odor, resembling that of beta-Ionone. More fruity than really floral, but not as tenacious as the Ionone.
Suggested for use in perfume compositions, but since it does not offer any new or unusual odor characteristics, and it cannot be produced in economical competition to beta-Ionone, there is little or no chance that it will ever become a standard shelf ingredient for the perfumer. . . . "
v. "869: DEHYDRO-beta-CYCLOCITRAL (Safranal)
2,6,6-trimethyl-4,4-cyclohexadiene-1-carboxaldehyde ##STR7##
Very powerful, sweet, green-floral and somewhat tobacco-herbaceous odor of good tenacity. In extreme dilution reminiscent of the odor of Safran (Saffron).
Interesting material for fresh topnotes, as a modifier for aldehydic-citrusy notes, as a green-floral topnote in flower fragrances, etc. It blends excellently with the aliphatic Aldehydes, with Oakmoss products and herbaceous oils. . . . "
Safranal and beta-cyclocitral are disclosed as volatile constituents of Greek Tobacco by Kimland et al., Phytochemistry 11 (309) 1972. Beta-cyclocitral is disclosed as a component of Burley Tobacco flavor by Demole and Berthet, Helv. chim. Acta. 55 Fasc 6, 1866 (1972).
Methods for producing enol esters are disclosed in the prior art. Thus, for example, heptaldehyde enol acetate is disclosed to be produced according to the process of reacting heptaldehyde with acetic anhydride in the presence of crystalline potassium acetate at reflux temperatures of 155.degree.-160.degree. C by Bedoukian, J.Am.Chem.Soc. 66, August, 1944, pages 1325-1327.
However, no disclosures exist in the prior art indicating the existence or implying the organoleptic uses of beta-cyclohomocitral enol esters or methods for synthesizing such compounds.